DE68924786T2 - (Trifluoromethyl) vinyl pyrethroid derivatives, their use as pesticides, process for their preparation and intermediates of this process. - Google Patents

Abstract

Products of formula (A): <IMAGE> in which the cyclopropane link is a (1R, trans) structure, the geometry of the double bond is Z, Z1 denotes an aryl radical optionally substituted by a halogen atom, R1 denotes one of the groups: <IMAGE> in which X1 denotes a hydrogen or fluorine atom, and R14 denotes a hydrogen atom or one of the methyl, ethynyl or cyano radicals.

Description

The present invention relates to trifluoromethylvinylpyrethrinoid derivatives, their preparation process, the intermediates of this process and their use as pesticides.

Publications EP-A-0061114 and EP-A-0019787 also describe trifluoromethylvinylpyrethrinoid derivatives with pesticidal properties.

The invention has products of the general formula (A)

in which the cyclopropane coupling has the structure (1R, trans), the geometry of the double bond is Z, Z₁ represents an aryl radical, optionally substituted by a halogen atom, and R₁ represents one of the groups

wherein X₁ represents a hydrogen or fluorine atom and R₁₄ represents a hydrogen atom or one of the radicals methyl, ethynyl or cyano, in particular those of formula (A) wherein Z₁ represents the 4- chlorophenyl radical, and especially the product of formula (A₁) 1R trans

and the product of formula (B₁) 1R trans

The invention also relates to the process for preparing the products of Examples 1 to 3. A product of formula (II)

in which Hal represents a bromine, chlorine or iodine atom, R represents an alkyl radical having up to 8 carbon atoms, optionally substituted by a trialkylsilyl radical or a benzyl radical and Z₁ is as defined in claim 1, the action of sodium trifluoroacetate in the presence of copper iodide to obtain a product of formula (I)

which is converted into the product of formula (A) as shown in Examples 1, 2 or 3.

The intermediates of formula (I) of the process with the following names:

- [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid methyl ester,

- [1R-(1α, 3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylic acid 2-(trimethylsilyl)- ethyl ester

are also the subject of the present invention.

The compounds of formula (II) are prepared according to developed methods, which are referred to as Preparation 1 and 2 in the later paragraphs.

The products of formula (A) defined above have interesting pesticidal properties which enable them to be used to combat parasites. This may, for example, involve combating parasites on plants, parasites in rooms and parasites on warm-blooded animals. The products of the invention can thus be used to combat parasites such as insects, nematodes and acarids on plants and animals.

The invention therefore relates to these compositions for their use in combating parasites on plants, parasites in rooms and parasites on warm-blooded animals.

These products can therefore be used in particular for the control of insects in agriculture, for example to control of aphids, butterfly larvae and beetles. They can be used in doses between 10 g and 300 g of active ingredient per hectare.

These products can also be used to control insects in rooms, especially flies, mosquitoes and cockroaches.

These products can also be used to control acarid parasites on plants.

These products can also be used to control nematode parasites on plants.

These products can also be used to combat acarid parasites on animals, for example to combat ticks, and in particular ticks of the genus Boophilus, the genus Hyalomnia, the genus Amblyomnia and the genus Rhipicephalus, or to combat all types of mange, in particular sarcoptic mange, psoroptic mange and chorioptic mange.

The invention therefore relates to compositions intended for combating parasites on warm-blooded animals, parasites in rooms and parasites on plants, characterized in that they comprise at least one of the products defined above.

The invention relates in particular to insecticidal compositions comprising as active ingredient at least one of the products defined above.

The compositions according to the invention are prepared according to customary processes in the agricultural industry, the veterinary industry or the feed industry.

These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, burning strips, baits or other preparations such as they are classically used when using this type of connection.

In addition to the active ingredient, these compositions generally contain a carrier and/or a non-ionic surfactant which also ensures uniform dispersion of the components making up the mixture. The carrier used can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, an animal, vegetable or mineral oil, a powder such as talc, clays, silicates, diatomaceous earth or a combustible solid.

The insecticidal compositions according to the invention preferably contain 0.005% to 10% by weight of active ingredient.

According to a preferred embodiment for use in rooms, the compositions according to the invention are used in the form of incense compositions.

The compositions according to the invention can therefore advantageously be formed, for the non-active part, from a combustible insecticidal coil (or spiral), or from a non-combustible fibrous substrate. In this last case, the fumigated product obtained after incorporation of the active ingredient is placed in an apparatus which is heated like an electric mosquito repeller.

In the case of using an insecticidal snake, the inert carrier may be composed of, for example, pyrethrum pith, tabu powder (or powder of the leaves of Machilus Thumbergii), pyrethrum stem powder, cedar leaf powder, wood powder (such as pine sawdust), starch and coconut shell powder. The dosage of active ingredient may be, for example, 0.03% to 1% by weight.

In the case where a non-combustible fibrous carrier is used, the dosage of active ingredient can be, for example, 0.03% to 95% by weight.

The compositions according to the invention for use in rooms can also be obtained by preparing a sprayable oil based on the active ingredient and by impregnating with this oil the wick of a lamp which is then burned.

The concentration of the active ingredient incorporated into the oil is preferably 0.03% to 95% by weight.

The invention also relates to acaricidal compositions comprising as active ingredient at least one of the products of formula (I) defined above.

The invention also relates to nematicidal compositions comprising as active ingredient at least one of the products of formula (I) defined above.

One or more other pesticidal agents may optionally be added to the insecticidal compositions of the invention, as well as to the acaricidal and nematicidal compositions. The acaricidal and nematicidal compositions may in particular be in the form of powders, granules, suspensions, emulsions and solutions.

For acaricidal application, it is preferable to use wettable foliar powders containing 1 to 80% or foliar liquids containing 1 to 500 g/l of active ingredient. Foliar powders containing 0.05 to 3% of active ingredient can also be used.

For nematicidal application, it is preferable to use liquids for treating the soil that contain 300 to 500 g/l of active ingredient.

The acaricidal and nematicidal compositions according to the invention are preferably used in dosages between 1 and 100 g of active ingredient per hectare.

The invention also relates to acaricidal compositions intended for combating acarid parasites on warm-blooded animals, in particular ticks and mange, characterized in that they comprise as active ingredient at least one of the products of formula (I) defined above.

In order to increase the biological activity of the products according to the invention, it is possible to add to them classical synergists used for the same case, such as 1-(2,5,8-trioxododecyl)-2-propyl-4,5-methylenedioxybenzene (or piperonyl butoxide), or N-(2-ethylheptyl)-5-bicyclo[2,2-1]heptene-2,3-dicarboximide, or piperonyl bis-2-(2'-n-butoxyethoxy)ethyl acetal (or tropital).

When it comes to combating acarid parasites in animals, the products according to the invention are very often incorporated into the feed compositions, in association with a feed mixture adapted to the animal's diet. The feed mixture may vary according to the animal species and may comprise cereals, sugars and grains, soya, peanut and sunflower oil cakes, animal meal, for example fish meal, synthetic amino acids, mineral salts, vitamins and antioxidants. The invention also relates to compositions intended for animal feeding, comprising as active ingredient at least one of the products of formula (I) defined above.

It can also be stated that the products of the invention can be used as biocides or as growth regulators.

The invention also relates to associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient, on the one hand, at least one of the compounds of general formula (I) and, on the other hand, at least one pyrethrinoid ester selected from the esters of allethrolon, 3,4,5,6-tetrahydrophthalimide-methyl alcohol, (5-benzyl-3-furyl)-methyl alcohol, 3-phenoxy-benzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols with chrysanthemic acids, from the esters of (5-benzyl-3-furyl)-methyl alcohol with the 2,2-dimethyl-3-(2-oxo-3-tetrahydrothio-phenylidene-methyl)-cyclopropanecarboxylic acids, from the esters of 3-phenoxy-benzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols with the 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids, from the esters of α-cyano-3-phenoxybenzyl alcohol with the 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acids, by the esters of 3-phenoxybenzyl alcohol with 2-para-chlorophenyl-2-isopropyl-acetic acids, and by the esters of allethrolones, 3,4,5,6-tetrahydrophthalimide-methyl alcohol, (5-benzyl-3-furyl)-methyl alcohol, 3-phenoxybenzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols with the 2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropanecarboxylic acids, wherein "halogen" represents a fluorine, chlorine or bromine atom.

The associations according to the invention are of particular importance because, thanks to the polyvalence of their action, they enable the control of a broad spectrum of parasites and, in some cases, show a synergistic effect.

The invention relates to pesticidal compositions as defined above, characterized in that they also comprise a pyrethrinoid synergist.

Synergists classically used for the same case include 1-(2,5,8-trioxododecyl)-2-propyl-4,5-methylenedioxybenzene (or piperonyl butoxide), or N-(2-ethylheptyl)-bicyclo[2,2-5]heptene-2,3-dicarboximide, or piperonyl bis-2-(2'- n-butoxyethoxy)ethyl acetal (tropital).

The following examples illustrate the invention.

EXAMPLE 1 : {1R-[1α(R*),3β]}-2,2-dimethyl-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-cyclopropanecarboxylic acid 1-(6-phenoxy-2-pyridyl)ethyl ester Step A : [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1- propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid methyl ester

Dissolve 2.95 g of [1R-(1α,3β)]-3-[(Z)-2-bromo-2-(4-chlorophenyl)ethenyl]-2,2-dimethylcyclopropanecarboxylic acid methyl ester (Preparation 1) and 4.68 g of sodium trifluoroacetate in 30 cm3 of N-methylpyrrolidone. Then add 3.27 g of copper iodide and heat for 6 hours at a temperature of about 160 °C. Allow to return to room temperature, filter, rinse and distill. A residue is obtained which is extracted with isopropyl ether. Wash, dry and evaporate to dryness. 3.94 g of product is obtained which is chromatographed on silica eluting with a hexane/isopropyl ether mixture (95/5). You get 2.22 g of the desired product.

NMR spectrum CDCl3:

Protons of methyl pairs 1.25 - 1.35 ppm

aromatic protons 7.13 7.5 ppm

ethylenic protons 5.63 5.80 ppm

Protons from carbon in position 3 of cyclopropane 2.33 - 2.75 ppm

Protons from carbon in position 1 of cyclopropane 1.69 - 1.78 ppm

Protons of CO₂-CH₃ 3.75 ppm

Step B : {1R-[1α(R*),3β]}-2,2-dimethyl-3-[(Z)-2-(4-chlorophenyl)- 3,3,3-trifluoro-1-propenyl]-cyclopropanecarboxylic acid 1-(6-phenoxy-2- pyridyl)-ethyl ester

Dissolve 0.85 g of the product prepared in step A in 3.75 cm³ of an N-sodium hydroxide solution. The resulting solution is then stirred for 7 hours at 40 ºC. It is poured into an ice-water mixture, 4 cm³ of an N-hydrochloric acid solution is added, the mixture is washed with water and with a saturated sodium chloride solution, dried and evaporated to dryness. 0.84 g of product is obtained, which is dissolved in 4 cm³ of methylene chloride together with 540 mg of (R)-6-(3-phenoxy)-α-methyl-2-pyridine-methanol. It is then cooled in an ice bath and a solution of 520 mg of dicyclohexylcarbodiimide, 8 mg of 4-dimethylaminopyridine and 3 cm³ of methylene chloride is added. The mixture is then stirred for 5 minutes in an ice bath and overnight at ambient temperature. It is filtered, rinsed with isopropyl ether and evaporated to dryness. 1.38 g of product are obtained, which is chromatographed on silica, eluting with a mixture of hexane and isopropyl ether (8/2). 1 g of the desired product is obtained.

[α]D = +98º ± 2º (c = 1 %)

Preparation 1: [1R-(1α,3β)]-3-[(Z)-2-bromo-2-(4-chlorophenyl)- ethenyl]-2,2-dimethyl-cyclopropanecarboxylic acid methyl ester and corresponding isomer 1R-[1α,3β(E)]

Dissolve 7.8 g of methyl (1R trans)-3-formyl-2,2-dimethylcyclopropanecarboxylate and 17.7 g of [bromo-(4-chlorophenyl)methyl]-dimethylphosphonate in 70 cm³ of tetrahydrofuran. Then cool to -40 ºC and add 6.16 g of potassium tert-butoxide in solution in 60 cm³ of tetrahydrofuran over 45 minutes. Then stir the solution obtained for 1 hour at -40 ºC/-45 ºC. Pour into an aqueous saturated solution of sodium acid phosphate, extract with isopropyl ether, wash, dry and evaporate to dryness. In this way, 18.7 g of product are obtained, which is chromatographed on silica, eluting with a hexane/isopropyl ether mixture (95/5). 2.97 g of isomer Z (17%) are obtained.

NMR spectrum CDCl&sub3; 60MHz :

aromatic protons 7.16 to 7.68 ppm

Vinyl proton 5.87 - 6 ppm

Protons of methyl pairs 1.23 - 1.35 ppm

Protons of CO₂-CH₃ 3.7 ppm

Protons in 1 of cyclopropane 1.63 - 1.73 ppm

Protons in 3 of cyclopropane 2.35 - 2.56 ppm

On the other hand, 5.91 g of isomer (34.5 %) is obtained

NMR spectrum CDCl&sub3; 60MHz :

aromatic protons 7.32 ppm

Vinyl proton 5.85 - 5.98 ppm

Protons of methyl pairs 1.17 - 1.22 ppm

Protons in 1 of cyclopropane 1.52 ppm

Protons in 3 of cyclopropane 1.87 - 2.1 ppm

EXAMPLE 2 : {1R-[1α(S*),3β]}-2,2-dimethyl-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-cyclopropanecarboxylic acid cyano-(4-fluoro-3-phenoxy-phenyl)-methyl ester Step A : [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1- propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid 2-(trimethylsilyl)- ethyl ester

Dissolve 3.06 g of [1R-(1α,3β)]-3-[(Z)-2-bromo-2-(chlorophenyl)ethenyl]-2,2-dimethylcyclopropanecarboxylic acid 2-(trimethylsilyl)ethyl ester (Preparation 2) and 3.86 g of sodium trifluoroacetate in 30 cm3 of N-methylpyrrolidone. Then add 2.7 g of copper iodide and keep the reaction mixture at 160 °C for 6 hours. Allow to return to room temperature, filter, rinse, remove the impurities, extract with isopropyl ether, dilute with hexane, wash with a saturated sodium chloride solution, dry over sodium sulfate and evaporate to dryness. 3.3 g of product are obtained, which is chromatographed on silica, eluting with a hexane/toluene mixture (6/4). 1.69 g of the desired product are isolated, which is again chromatographed on silica, eluting with a hexane/isopropyl ether mixture (95/5). 1.35 g of the expected product are thus obtained.

NMR spectrum CDCl₃ ppm :

aromatic protons 7.08 to 7.42 ppm

Vinyl proton 5.62 - 5.8 ppm

Protons of methyl pairs 1.22 - 1.32 ppm

Protons from carbon in position 1 of cyclopropane 1.62 - 1.72 ppm

Protons from carbon in position 3 of cyclopropane 2.35 to 2.82 ppm

Protons in α of CO₂ 4.05 to 4.33 ppm

Protons in β of CO₂ 0.86 to 1.13 ppm

Step B : {1R-[1α(S*),3β]}-2,2-dimethyl-3-[(Z)-2-(4-chlorophenyl)- 3,3,3-trifluoro-1-propenyl]-cyclopropanecarboxylic acid cyano-(4-fluoro- 3-phenoxy-phenyl)-methyl ester

1.32 g of 2-(trimethylsilyl)ethyl [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate and 6.3 cm3 of a molar solution of tetrabutylammonium fluoride in tetrahydrofuran are stirred for 6 hours at ambient temperature. Then it is poured into an ice-water mixture, 1.55 cm3 of an N-hydrochloric acid solution is added, extraction with isopropyl ether, washing with a saturated sodium chloride solution, drying and evaporation to dryness. 1.1 g of product are obtained, which is dissolved in 6 cm3 of methylene chloride with 780 mg of (S)-α-cyano-4-fluoro-3-phenoxybenzyl alcohol. Then cool in an ice bath and add a solution of 650 mg of dicyclohexylcarbodiimide, 10 mg of 4-dimethylaminopyridine and 4 cm3 of methylene chloride. The mixture is then stirred for 5 minutes at 0 ºC ± 5 ºC and then for 1 hour at room temperature. Filter and rinse with isopropyl ether. 1.7 g of product are thus obtained, which is chromatographed on silica eluting with a hexane/isopropyl ether mixture (8/2). 416 mg of the desired product are obtained, melting at 78 ºC.

[α]D = +49º ± 1.5º (c = 1% CHCl₃).

Preparation 2 : [1R-(1α,3β)]-3-[(Z)-2-bromo-2-(4-chlorophenyl)- ethenyl]-2,2-dimethyl-cyclopropanecarboxylic acid 2-(trimethylsilyl)- ethyl ester and corresponding isomer E

Dissolve 2.84 g of (1R trans)-3-formyl-2,2-dimethylcyclopropanecarboxylic acid and 7.5 g of [bromo-(4-chlorophenyl)methyl]dimethylphosphonate in 20 cm3 of tetrahydrofuran. Then cool to -40 ºC/-45 ºC and add a solution of 5 g of potassium tert-butoxide in 25 cm3 of tetrahydrofuran over 25 minutes. Then stir the solution thus obtained for 1 hour at -40 ºC/-45 ºC. Pour into a saturated aqueous solution of sodium acid phosphate, extract with isopropyl ether, wash, dry and evaporate to dryness. This gives 7.3 g of residue, which is dissolved in 20 cm3 of methylene chloride. Then 2.85 cm3 of trimethylsilylethanol are added. Then 4.53 g of dicyclohexylcarbodiimide, 70 mg of 4-dimethylaminopyridine and 15 cm3 of methylene chloride are added at about 0 ºC. Then the mixture is stirred for 5 minutes in an ice bath and for 1 hour at ambient temperature. The mixture is filtered, rinsed with isopropyl ether and evaporated to dryness. 9 g of product are recovered, which is chromatographed using a hexane/isopropyl ether mixture (95/5). 3.11 g of isomer Z are obtained.

NMR spectrum CDCl3:

aromatic protons 7.15 - 7.52 ppm

Protons of methyl pairs 1.24 - 1.37 ppm

Vinyl proton 5.87 - 6 ppm

Protons of carbon in 3 of cyclopropane 2.33 - 2.55 ppm

Protons of carbon in 1 of cyclopropane 1.60 1.7 ppm

Protons in α of CO₂ 4.05 - 4.33 ppm

Protons in β of CO₂ 0.86 to 1.15 ppm

One also obtains 1.88 g of isomer E

NMR spectrum CDCl3:

aromatic protons 7.32 ppm

Protons of methyl pairs 1.17 1.22 ppm

Vinyl proton 5.87 - 6 ppm

Protons of carbon in 3 of cyclopropane 1.85 to 2.08 ppm

Protons of carbon in 1 of cyclopropane 1.47 - 1.57 ppm

Protons in α of CO₂ 3.96 - 4.25 ppm

Protons in β of CO₂ 0.8 - 1.08 ppm

EXAMPLE 3 : {1R-[1α(RS),3β]}-3-[(Z)-2-(4-chlorophenyl)-3,3,3- trifluoro-1-propenyl]-cyclopropanecarboxylic acid 1-(6-phenoxy-2-pyridyl)-ethyl ester

Proceed as in Example 1 but in Step B using 1.07 g (RS)-6-(3-phenoxy)-α-methyl-2-pyridinemethanol to obtain 3 g of product which is chromatographed on silica eluting with a hexane/isopropyl ether (9/1) mixture. 1.97 g of the expected product is recovered.

EXAMPLE 4 : Preparation of a soluble concentrate

Prepare a homogeneous mixture of:

Product of Example 1 ... 0.25 g

Piperonyl butoxide ... 1.00 g

Tween 80 ... 0.25 g

Topanol A ... 0.1 g

Water ... 98.4 g

EXAMPLE 5 : Preparation of an emulsifiable concentrate

Mix thoroughly:

Product of Example 2 ... 0.015 g

Piperonyl butoxide ... 0.5 g

Topanol A ... 0.1 g

Tween 80 ... 3.5 g

Xylene ... 95.885 g

EXAMPLE 6 : Preparation of an emulsifiable concentrate

Prepare a homogeneous mixture of:

Product of Example 1 ... 1.5 g

Tween 80 ... 20.0 g

Topanol A ... 0.1 g

Xylene ... 78.4 g

EXAMPLE 7 : Preparation of an incense composition

Mix in a homogeneous manner:

Product of Example 1 ... 0.25 g

Taboo powder ... 25.0 g

Powder of cedar leaves ... 40.00 g

Pinewood powder ... 33.75 g

Brilliant green ... 0.50 g

p-Nitrophenol ... 0.50 g

EXAMPLE 8 : Examples of compositions

Compositions of the following formulation were prepared:

Product of Example 1 ... 1700.00 g

Dimethylformamide ... 40.00 cm³

Olive oil ... 40.00 cm³

EXAMPLE 9 : Preparation of an emulsifiable concentrate

Mix thoroughly:

Product of Example 1 ... 0.015 g

Piperonyl butoxide ... 0.5 g

Topanol A ... 0.1 g

Xylene ... 99.385 g

EXAMPLE 10 : Preparation of an emulsifiable concentrate

Prepare a homogeneous mixture of:

Product of Example 2 ... 1.5 g

Tween 80 ... 20.0 g

Topanol A ... 0.1 g

Xylene ... 78.4 g

BIOLOGICAL EXAMINATION 1) Investigation of the lethal effect on houseflies

The insects tested are female houseflies aged 4 days. The procedure involves the topical application of 1 μl of acetone solution to the dorsal thorax of the insects using an ARNOLD micromanipulator. 50 individuals are used for one treatment. Mortality is monitored 24 hours after treatment.

The tests are carried out without synergist or with the addition of piperonyl butoxide (10 parts of synergist per 1 part of compound to be tested). The experimental results summarized in the following table are expressed in DL50 or the dose (in nanograms) required to kill 50% of the insects. Compound of Example DL₅₀ in ng/insect

2) Investigation of the lethal effect on Aphis cracivora

Adult individuals are used after 7 days and 10 aphids per concentration tested. A contact injection method is used. The treatment of a bean leaf is carried out using the Fisher gun, placing the leaf in a plastic Petri dish on a moistened round piece of paper. The treatment is carried out using 2 ml of acetone solution of the product to be tested (1 ml per leaf side)

The insect infestation is carried out after the leaf has dried. The insects are kept in contact with the leaf for one hour. The insects are then transferred to untreated leaves and mortality is checked after 24 hours.

The experimental results are summarized in the following table: Compound of Example CL₅₀₀ in mg/l

3) Investigation of acaricidal activity in animals a) Investigation of the effect on larvae of Boophilius Microplus

The substance to be tested is dissolved in a mixture of dimethylformamide, emulsifiers and Arcopal in such a way as to obtain an emulsifier concentration of 10%. This concentration is diluted with water to obtain solutions with the desired concentrations of 100, 10 and 1 ppm.

The various solutions mentioned above are sprayed onto the larvae of the Boophilus Microplus ticks of tropical cattle using a spray tower and After 24 hours, determine the percentage of mortality by counting the dead and living larvae.

The results are as follows: Dose in ppm Results % Mortality Product of Example

Conclusion:

The products of examples 1, 2 and 3 show a remarkable effect.

b) Investigation of the effect on the inhibition of tick reproduction Boophilus Microplus

Female Boophilus Microplus ready to lay eggs are immersed in the solutions prepared above for 5 minutes and then placed in a heated container to lay eggs.

You determine:

a - the percentage of ticks that have not laid eggs,

b - the quantity of eggs laid in relation to a control,

c - the percentage of hatched larvae.

The percentage of inhibition of reproduction is calculated depending on the figures obtained, with 100% indicating that the inhibition is complete and 0% indicating that the reproduction is identical to that obtained with the control animals.

You get Dose in ppm Results % Inhibition Product of Example

Conclusion:

The products of examples 1, 2 and 3 show a remarkable effect.

Claims (19)

1. The products of formula (A) in which the cyclopropane coupling has the structure (1R, trans), the geometry of the double bond is Z, Z₁ represents an aryl radical, optionally substituted by a halogen atom, and R₁ represents one of the groups wherein X₁ represents a hydrogen or fluorine atom and R₁₄ represents a hydrogen atom or one of the radicals methyl, ethynyl or cyano. 2. The products of formula (A) as defined in claim 1, wherein Z₁ represents the 4-chlorophenyl radical. 3. The product of formula (A₁) 1R trans 4. The product according to claim 3, wherein the chiral carbon of the group cyano-(4-fluoro-3-phenoxyphenyl)-methyl has the configuration S. 5. The product of formula (B₁) 1R trans 6. The product of formula (B1) as defined in claim 5, wherein the chiral carbon of the group l-(6-phenoxy-2-pyridyl)ethyl has the configuration R or RS. 7. Process for the preparation of the product of formula (A1) as defined in claim 4, in which the chiral carbon of the group cyano-(4-fluoro-3-phenoxyphenyl)-methyl has the configuration S characterized in that a) preparing an intermediate by reaction of [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2- dimethylcyclopropanecarboxylic acid 2-(trimethylsilyl)ethyl ester and tetrabutylammonium fluoride, and b) adding this intermediate to the (S)-α-cyano-4-fluoro-3-phenoxybenzyl alcohol in methylene chloride, in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine. 8. Process for the preparation of the product (B₁) as defined in claim 6, in which the chiral carbon of the group 1-(6-phenoxy- 2-pyridyl)-ethyl has the configuration R, characterized in that a) the [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1- propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid methyl ester is treated with sodium hydroxide, and b) the product obtained in this way is isolated and reacted with (R)-6- (3-phenoxy)-α-methyl-2-pyridine-methanol in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine. 9. Process according to claim 8 for the preparation of the product of formula (B1) as defined in claim 6, wherein the chiral carbon of the group 1-(6-phenoxy-2-pyridyl)ethyl has the configuration RS, using (RS)-6-(3-phenoxy)-α-methyl-2-pyridine-methanol. 10. Use of the compounds of formula (A) as defined in any of claims 1 to 6 for combating parasites on plants, parasites in rooms and parasites on warm-blooded animals. 11. Compositions for combating parasites on plants, parasites in rooms and parasites on warm-blooded animals, characterized in that they comprise as active ingredient at least one of the products defined in any one of claims 1 to 6. 12. Insecticidal compositions comprising as active ingredient at least one of the products defined in any one of claims 1 to 6. 13. Acaricidal compositions comprising as active ingredient at least one of the products defined in any one of claims 1 to 6. 14. Nematicidal compositions comprising as active ingredient at least one of the products defined in any one of claims 1 to 6. 15. Acaricidal compositions for combating parasites on warm-blooded animals, in particular ticks and mange, characterized in that they comprise as active ingredient at least one of the products defined in any one of claims 1 to 6. 16. Compositions for animal feeding comprising as active ingredient at least one of the products defined in any one of claims 1 to 6. 17. Associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient on the one hand at least one of the compounds of formula (A) as defined in claim 1 and on the other hand at least one pyrethrinoid ester chosen from the group consisting of the esters of allethrolones, 3,4,5,6-tetrahydrophthalimide-methyl alcohol, (5-benzyl-3-furyl)-methyl alcohol, 3-phenoxy-benzyl alcohol and the α-cyano-3- phenoxybenzyl alcohols with chrysanthemic acids, by the esters of (5-benzyl-3-furyl)-methyl alcohol with the 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidene-methyl)-cyclopropanecarboxylic acids, by the esters of 3-phenoxybenzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols with the 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids, by the esters of α-cyano-3-phenoxybenzyl alcohols with the 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acids, by the esters of 3-phenoxybenzyl alcohol with 2-para-chlorophenyl-2-isopropyl-acetic acids, and by the esters of allethrolones, 3,4,5,6-tetrahydrophthalimide-methyl alcohol, (5-benzyl-3-furyl)-methyl alcohol, 3-phenoxy-benzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols with the 2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropanecarboxylic acids, wherein "halogen" represents a fluorine, chlorine or bromine atom. 18. Compositions as defined in any one of claims 11 to 17, characterized in that they further comprise a synergist of the pyrethrinoids. 19. The intermediates of formula (I), whose names follow: - [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid methyl ester, - [1R-(1α,3β)]-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoro-1-propenyl]-2,2-dimethyl-cyclopropanecarboxylic acid 2-(trimethylsilyl)- ethyl ester.